CN107434846A - 一种耐高温聚氨酯硬质泡沫材料及其制备方法 - Google Patents

一种耐高温聚氨酯硬质泡沫材料及其制备方法 Download PDF

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CN107434846A
CN107434846A CN201710854537.8A CN201710854537A CN107434846A CN 107434846 A CN107434846 A CN 107434846A CN 201710854537 A CN201710854537 A CN 201710854537A CN 107434846 A CN107434846 A CN 107434846A
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陆璘
刘方辉
饶安梅
陈建平
汪鑫
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Guizhou Aerospace Tianma Electrical Technology Co Ltd
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Abstract

本发明涉及聚氨酯泡沫材料技术领域,尤其是一种耐高温聚氨酯硬质泡沫材料及其制备方法,经过将聚醚多元醇组合料和改性异氰酸酯作为原料制备聚氨酯硬质泡沫材料,并将异氰酸酯是采用改性剂改性制得的噁唑烷酮环异氰酸酯改性体后混合,使得在250℃高温下,材料的机械性能较高,尺寸稳定性较强,能够在200℃下长期使用,确保材料长期贮存的可靠性。

Description

一种耐高温聚氨酯硬质泡沫材料及其制备方法
技术领域
本发明涉及聚氨酯泡沫材料技术领域,尤其是一种耐高温聚氨酯硬质泡沫材料及其制备方法。
背景技术
硬质聚氨酯泡沫材料,其具有多种优异的性能,被广泛应用于各个领域;并且,现有技术中,对于硬质聚氨酯泡沫材料的研究技术也相对较多。但大多数技术所研究出来的硬质聚氨酯泡沫材料,其只能在100℃下使用,导致其使用范围受到局限性。
有研究者,将聚异氰脲酸酯改性聚氨酯泡沫材料,能够使得聚氨酯泡沫材料在150℃的温度下,长期使用,与未经过改性处理的聚氨酯泡沫材料相比,其耐温性能大幅度的提高,其具体实现的原理是:随着异氰尿酸酯在聚合过程中的环数目增多,将其用于改性聚氨酯泡沫材料后,耐温性能也逐步增大,能够有效的改善其耐温性能;但是,随着异氰尿酸酯在聚合过程中的环数目增多,将其用于改性聚氨酯泡沫材料,脆性也随着增大,并且耐高温性能依然不足,使得得到的聚氨酯泡沫材料的使用范围依然受到局限。
基于此,本研究者经过对硬质聚氨酯泡沫材料进行研究,将异氰酸酯是采用改性剂改性制得的噁唑烷酮环异氰酸酯改性体,并与聚醚多元醇组合料混合制备聚氨酯硬质泡沫材料,使得其耐高温性能大幅度的提高,并且在长期贮存使用过程中不会发生变形、龟裂、机械性能下降等现象,环境适应性能较好;为硬质聚氨酯泡沫材料制备提供了一种新思路。
发明内容
为了解决现有技术中存在的上述技术问题,本发明提供一种耐高温聚氨酯硬质泡沫材料及其制备方法。
本发明创造的目的之一是提供一种耐高温聚氨酯硬质泡沫材料,由聚醚多元醇组合料和改性异氰酸酯组成,其中聚醚多元醇组合料为三羟基聚醚、多羟基氨基聚醚、一氟二氯乙烷、水溶性硅油、三乙烯二胺、甲基磷酸二甲酯、抗老化剂混合而成,改性异氰酸酯是采用改性剂改性制得的噁唑烷酮环异氰酸酯改性体。
优选,所述的改性剂为双酚A型环氧树脂。
优选,所述的改性剂为e-44双酚A型环氧树脂。
优选,所述的异氰酸酯是以4,4’-MDI异构体为主要成份的二苯基甲烷二异氰酸酯。
优选,所述的异氰酸酯是4,4’-MDI异构体的二苯基甲烷二异氰酸酯。
优选,所述的改性剂,在改性异氰酸酯时,与异氰酸酯混合质量比为1:13。
优选,聚醚多元醇组合料和改性异氰酸酯的质量比为10:26-31。
优选,所述的聚醚多元醇组合料,原料成分组成为三羟基聚醚50-80g、多羟基氨基聚醚20-50g、一氟二氯乙烷8-12g、水溶性硅油0.5-4.5g、三乙烯二胺2.5-5g、甲基磷酸二甲酯8-15g、抗老化剂0.5-2g。
本发明创造的目的之二是提供上述的耐高温聚氨酯硬质泡沫材料制备方法,包括以下步骤:
(1)将聚醚多元醇组合料原料混合,在1000-1500r/min下,搅拌混合2min,得到聚醚多元醇组合料;
(2)将异氰酸酯与改性剂按照质量比为13:1混合,加入占改性剂质量1%的Zn Br2催化剂,于150℃下,搅拌作用25min,冷却至室温,得到改性异氰酸酯;
(3)将聚醚多元醇组合料与改性异氰酸酯混合,在2000-3500r/min下,搅拌混合20±5s,注入模具,发泡成型,即得耐高温聚氨酯硬质泡沫材料。
本发明创造的目的之三是提供一种用于耐高温聚氨酯硬质泡沫材料的异氰酸酯改性方法,将以4,4’-MDI异构体为主要成份的二苯基甲烷二异氰酸酯与e-44双酚A型环氧树脂按照质量比为13:1混合,并加入占e-44双酚A型环氧树脂质量1%的Zn Br2催化剂,于150℃下,搅拌作用25min,冷却至室温,得到噁唑烷酮环异氰酸酯改性体。
与现有技术相比,本发明创造的技术效果体现在:
经过将聚醚多元醇组合料和改性异氰酸酯作为原料制备聚氨酯硬质泡沫材料,并将异氰酸酯是采用改性剂改性制得的噁唑烷酮环异氰酸酯改性体后混合,使得在250℃高温下,材料的机械性能较高,尺寸稳定性较强,能够在200℃下长期使用,确保材料长期贮存的可靠性。
具体实施方式
下面结合具体的实施方式来对本发明的技术方案做进一步的限定,但要求保护的范围不仅局限于所作的描述。
实施例1
称取三羟基聚醚50g、多羟基氨基聚醚40g、一氟二氯乙烷10g、水溶性硅油1g、三乙烯二胺4g、甲基磷酸二甲酯12g、抗老化剂1.5g,在1500r/min下,搅拌混合2min,得聚醚多元醇组合料;
将异氰酸酯与改性剂按照质量比为13:1混合,加入占改性剂质量1%的Zn Br2催化剂,于150℃下,搅拌作用25min,冷却至室温,得到改性异氰酸酯;
称取改性异氰酸酯260g,注入聚醚多元醇组合料中,在3000r/min下,搅拌混合20±5s,注入模具中,发泡成型,得耐高温硬质聚氨酯泡沫材料。
将该材料制成:长×宽×高=(100×100×25)mm试样,在250℃高温存放不同时间,其性能变化见表1。
表1容重为100kg/m3耐高温硬质聚氨酯泡沫材料250℃存放时间性能变化情况
由表1数据显示,该实施例制备的材料,其在250℃高温下,其材料尺寸和拉伸性能均具有较高的稳定性。
实施例2
称取三羟基聚醚60g、多羟基氨基聚醚50g、一氟二氯乙烷12g、水溶性硅油4.5g、三乙烯二胺2.5g、甲基磷酸二甲酯8g、抗老化剂2g,在1000r/min下,搅拌混合2min,得聚醚多元醇组合料;
将异氰酸酯与改性剂按照质量比为13:1混合,加入占改性剂质量1%的Zn Br2催化剂,于150℃下,搅拌作用25min,冷却至室温,得到改性异氰酸酯;
称取改性异氰酸酯310g,注入聚醚多元醇组合料中,在3500r/min下,搅拌混合20±5s,注入模具中,发泡成型,得耐高温硬质聚氨酯泡沫材料。
将该材料制成:长×宽×高=(100×100×25)mm试样,在250℃高温存放不同时间,其性能变化见表2。
表2容重为100kg/m3耐高温硬质聚氨酯泡沫材料250℃存放时间性能变化情况
由表2数据显示,该实施例制备的材料,其在250℃高温下,其材料尺寸和拉伸性能均具有较高的稳定性。
实施例3
称取三羟基聚醚80g、多羟基氨基聚醚20g、一氟二氯乙烷8g、水溶性硅油0.5g、三乙烯二胺5g、甲基磷酸二甲酯15g、抗老化剂0.5g,在1300r/min下,搅拌混合2min,得聚醚多元醇组合料;
将异氰酸酯与改性剂按照质量比为13:1混合,加入占改性剂质量1%的ZnBr2催化剂,于150℃下,搅拌作用25min,冷却至室温,得到改性异氰酸酯;
称取改性异氰酸酯285g,注入聚醚多元醇组合料中,在2000r/min下,搅拌混合20±5s,注入模具中,发泡成型,得耐高温硬质聚氨酯泡沫材料。
将该材料制成:长×宽×高=(100×100×25)mm试样,在250℃高温存放不同时间,其性能变化见表3。
表3容重为100kg/m3耐高温硬质聚氨酯泡沫材料250℃存放时间性能变化情况
由表3数据显示,该实施例制备的材料,其在250℃高温下,其材料尺寸和拉伸性能均具有较高的稳定性。
本发明创造为了研究异氰酸酯成分的影响,对各种异构体异氰酸酯进行研究,并采用改性剂进行改性添加,其得出:采用异氰酸酯是以4,4’-MDI异构体为主要成份的二苯基甲烷二异氰酸酯作为原料制备的耐高温硬质聚氨酯泡沫材料,其能够在200℃下长期贮存,使用寿命达到10年以上,并且使用过程不会发生变形、龟裂、机械性能下降等现象,环境适应性能较好。而且,经过对异氰酸酯采用异构体为4,4’-MDI的纯异构体作为原料制备耐高温硬质聚氨酯泡沫材料,其耐高温性能得到增强,并且在300℃左右,处理80h,其体积变化不显著,而且,拉伸强度维持在6MPa左右,具有较优的性能。

Claims (10)

1.一种耐高温聚氨酯硬质泡沫材料,由聚醚多元醇组合料和改性异氰酸酯组成,其中聚醚多元醇组合料为三羟基聚醚、多羟基氨基聚醚、一氟二氯乙烷、水溶性硅油、三乙烯二胺、甲基磷酸二甲酯、抗老化剂混合而成,其特征在于,改性异氰酸酯是采用改性剂改性制得的噁唑烷酮环异氰酸酯改性体。
2.如权利要求1所述的耐高温聚氨酯硬质泡沫材料,其特征在于,所述的改性剂为双酚A型环氧树脂。
3.如权利要求1或2所述的耐高温聚氨酯硬质泡沫材料,其特征在于,所述的改性剂为e-44双酚A型环氧树脂。
4.如权利要求1所述的耐高温聚氨酯硬质泡沫材料,其特征在于,所述的异氰酸酯是以4,4’-MDI异构体为主要成份的二苯基甲烷二异氰酸酯。
5.如权利要求1或4所述的耐高温聚氨酯硬质泡沫材料,其特征在于,所述的异氰酸酯是4,4’-MDI异构体的二苯基甲烷二异氰酸酯。
6.如权利要求1所述的耐高温聚氨酯硬质泡沫材料,其特征在于,所述的改性剂,在改性异氰酸酯时,与异氰酸酯混合质量比为1:13。
7.如权利要求1所述的耐高温聚氨酯硬质泡沫材料,其特征在于,聚醚多元醇组合料和改性异氰酸酯的质量比为10:26-31。
8.如权利要求1或7所述的耐高温聚氨酯硬质泡沫材料,其特征在于,所述的聚醚多元醇组合料,原料成分组成为三羟基聚醚50-80g、多羟基氨基聚醚20-50g、一氟二氯乙烷8-12g、水溶性硅油0.5-4.5g、三乙烯二胺2.5-5g、甲基磷酸二甲酯8-15g、抗老化剂0.5-2g。
9.如权利要求1-8任一项所述的耐高温聚氨酯硬质泡沫材料制备方法,其特征在于,包括以下步骤:
(1)将聚醚多元醇组合料原料混合,在1000-1500r/min下,搅拌混合2min,得到聚醚多元醇组合料;
(2)将异氰酸酯与改性剂按照质量比为13:1混合,加入占改性剂质量1%的Zn Br2催化剂,于150℃下,搅拌作用25min,冷却至室温,得到改性异氰酸酯;
(3)将聚醚多元醇组合料与改性异氰酸酯混合,在2000-3500r/min下,搅拌混合20±5s,注入模具,发泡成型,即得耐高温聚氨酯硬质泡沫材料。
10.一种用于耐高温聚氨酯硬质泡沫材料的异氰酸酯改性方法,其特征在于,将以4,4’-MDI异构体为主要成份的二苯基甲烷二异氰酸酯与e-44双酚A型环氧树脂按照质量比为13:1混合,并加入占e-44双酚A型环氧树脂质量1%的Zn Br2催化剂,于150℃下,搅拌作用25min,冷却至室温,得到噁唑烷酮环异氰酸酯改性体。
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